Diaryl derivatives and their use as crop protection agents

ABSTRACT

Diaryl derivatives of the general formula I ##STR1## where A is ═CHOR 1 , ═CHSR 1 , ═CHR 1  , ═CHCl or ═NOR 1 , 
     B is OR 2 , SR 2  or NR 2  R 3  and 
     Het is a mono-, di- or trinuclear aromatic five- or six-membered heterocyclic structure which is unsubstituted or substituted by R, 
     R 1 , R 2 , R 3 , R 4 , R 5  are identical or different and each is hydrogen or alkyl, and 
     U, V, W are identical or different and each is halogen, alkyl or alkoxy, and fungicides containing these compounds.

This is a Division of application Ser. No. 08/231,487, filed on Apr. 22,1994, now U.S. Pat. No. 5,594,020.

The present invention relates to novel diaryl derivatives of the generalformula I ##STR2## where: A is ═CHOR¹, ═CHSR¹, ═CHR¹, ═CHCl or ═NOR¹,

B is OR², SR² or NR² R³,

Het is a mono-, di- or trinuclear, five- or six-membered heterocyclicstructure which may carry from one to three radicals R,

R is halogen, nitro, cyano, CO₂ R⁴, NR⁴ R⁵, CONR⁴ R⁵, S(O)_(n) R⁴P(O)(OR⁴)₂, substituted or unsubstituted C₁ -C₆ -alkyl, C₁ -C₄-haloalkyl, substituted or unsubstituted C₃ -C₆ -cycloalkyl, C₁ -C₄-alkoxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio-C₁ -C₄ -alkyl, substituted orunsubstituted C₂ -C₆ -alkenyl, substituted or unsubstituted C₂ -C₆-alkynyl, C₁ -C₆ -alkoxy, C₁ -C₄ -thioalkoxy, substituted orunsubstituted benzylthio,

C₁ -C₄ -alkylcarbonyl, substituted or unsubstituted phenylcarbonyl,substituted or unsubstituted aryl, substituted or unsubstituted aryloxy,substituted or unsubstituted arylthio, substituted or unsubstitutedaryl-C₁ -C₄ -alkyl, substituted or unsubstituted aryl-C₂ -C₄ -alkenyl,substituted or unsubstituted aryl-C₂ -C₄ -alkynyl, substituted orunsubstituted aryloxy-C₁ -C₄ -alkyl, substituted or unsubstitutedarylthio-C₁ -C₄ -alkyl, substituted or unsubstituted hetaryl,substituted or unsubstituted hetaryloxy, substituted or unsubstitutedhetaryl-C₁ -C₄ -alkyl, substituted or unsubstituted hetaryl-C₂ -C₄-alkenyl, substituted or unsubstituted hetaryloxy-C₁ -C₄ -alkyl,

"substituted or unsubstituted" denoting the radicals halogen, cyano,nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄-haloalkoxy or C₁ -C₄ -alkoximino-C₁ -C₂ -alkyl and

where

n is 0, 1 or 2,

R¹, R², R³, R⁴, R⁵ are identical or different and each is hydrogen or C₁-C₄ -alkyl and

U, V, W are identical or different and each is halogen, C₁ -C₄ -alkyl orC₁ -C₄ -alkoxy, and methods of combatting pests, especially fungi,insects, nematodes and mites, with these compounds.

The use of methyl 2-phenyl-3-methoxyacrylate or phenylglyoxylic acidmethyl ester-O-methyloximes substituted in the phenyl moiety at the2-position by hetarylmethyl, hetarylethenyl, hetaryloxy, phenyl orhetaryloxymethyl as fungicides has been disclosed (EP-A 178 826, EP-A350 691, EP-A 363 818, EP-A 378 755 and EP-A 254 426). However, theirfungicidal action is unsatisfactory.

The object of the invention was to provide novel compounds with improvedproperties.

We have found that this object is achieved by the novel compounds I. Wehave further found that the compounds I have an excellent fungicidal,insecticidal, nematicidal and acaricidal action. The fungicidal andinsecticidal action is preferred.

The preparation of the compounds of the general formula I is describedbelow:

As an abbreviation for the group ##STR3##

The novel compounds of the general formula Ib can be prepared forinstance by reacting, in conventional manner, a bromoaromatic compoundof the general formula 1 with a heteroaromatic tin compound 2 or aheteroaromatic boron compound 3 in the presence of a transition metalcatalyst (TM), preferably a nickel or palladium compound such as NiCl₂,Pd(OAc)₂, PdCl₂ or Pd(PPh₃)₄ (see, for example, Synthesis, 693 (1987);T. R. Bailey, Tetrah. Lett. 4407 (1986); Y. Yamamoto, Heterocycles16,1161 (1981)). The heteroaromatic tin and boron compounds are known ormay be prepared analogously to known methods. ##STR4##

Another way of preparing the compounds of the general formula I, Hetdenoting an aromatic five-membered heterocyclic structure, is3+2!-dipolar cycloaddition.

In this way, the acetylene derivatives 4 can be reacted in conventionalmanner with 1,3-dipoles 5 to give the desired aromatic five-memberedheterocyclic structures 6 (see Houben-Weyl, vol. 5/2a, pp. 830 et seq.(1977)). ##STR5##

For example the following derivatives may be prepared in this way:

--The isoxazole derivatives 8 and 9 are obtained by reaction of nitrileoxides 7. ##STR6## --It is also possible to react an oxime of thegeneral formula 10 with an acetylene 11 in the presence of hypochlorite.The isoxazoles 12 and 13 are obtained. ##STR7## --The triazoles of thegeneral formula 15 may be prepared by reaction of acetylenes 4 withazides 14: ##STR8## --The pyrroles 17 and 18 may be prepared by reactionof diazoalkanes 16. ##STR9##

Oxadiazole derivatives 22 may for instance be prepared fromacyl-hydrazones 21, which in turn are obtained from aldehydes 19 byreaction with hydrazides 20 (cf. EP 499823). ##STR10## --Oxidation ofthe hydrazones 21 to the oxadiazoles 22 is carried out for instance withlead tetraacetate or with bromine in a solvent or diluent such asmethylene chloride or chloroform (cf. for example Synthesis, 411, 1986).

A further possibility of preparing the novel compounds of the formula Iis shown in Scheme 8: ##STR11## --The aldehydes may be converted inconventional manner via the cyanohydrins 26 into the mandelic acidderivatives 29 (cf. for example U.S. Pat. No. 2,892,847), which can beoxidized to the keto esters 30 analogously to known methods, for examplewith sodium hypochlorite (cf. for example EP-A 140 454).

--The keto esters 30 may also be prepared in one stage from the halogenderivatives 24 via Grignard or organometallic intermediate stages (cf.for example Synth. Comm. 20, 1781 (1990).

--A further possibility of preparing the keto esters is to convert theacyl chlorides 25 into the benzoyl cyanides 28, which can then beconverted in a Pinner reaction into the keto esters 30 (cf. for exampleEP-A 493 711).

The esters of the general formula I are obtained from the keto esters 30prepared in this way by ##STR12## a) converting the keto esters 23 intothe oxime ethers Ic with methoxyaminohydrochloride, or ##STR13## b) byreacting the keto esters 23with the ylids 31 along the lines of a Wittigor a Wittig-Horner reaction.

The thiol esters or the methylamides may be obtained in conventionalmanner as follows from the esters Ie prepared in this way: ##STR14##

The thiol esters Ig can be obtained in conventional manner via theintermediate compounds acid 32 and acyl chloride 33 (cf. EP-A 432 503).

The methyl amides If may be prepared either directly by aminolysis ofthe esters Ie (cf. EP-A 477 631) or by aminolysis of the acyl chlorides33 (EP-A 477 631).

Because of the C═C or C═N double bonds, the novel compounds of thegeneral formula I may be obtained as an E/Z mixture of isomers. Theseisomers can be separated in conventional manner, e.g., bycrystallization or chromatography, into their individual components.Both the individual isomeric compounds and mixtures thereof areencompassed by the invention and can be used as pesticides.

The radicals in the general formula I have for example the followingmeanings:

A is ═CHOR¹, ═CHSR¹, ═CHR¹, ═CHCl or ═NOR¹,

B is OR², SR² or NR² R³ and the term

Het is a mono-, di- or trinuclear aromatic five- or six-memberedheterocycle, e.g., pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl,triazinyl, tetrazinyl, quinolinyl, phenazinyl, thienyl, furyl, pyrryl,imidazolyl, oxazolyl, isoxazolyl, thiazolyl, thiadiazolyl, oxadiazolyl,tetrazolyl, benzothienyl, benzofuranyl, indolyl, benzimidazolyl,benzooxazolyl, benzothiazolyl or benzisoxazolyl, which is unsubstitutedor substituted by from one to three of the radicals R, where

R is identical or different and is hydrogen, halogen (e.g., fluoro,chloro, bromo, iodo), nitro, cyano, NR⁴ R⁵, CO₂ R⁴, CONR⁴, R⁵, S(O)_(n)R⁴ where n=0, 1 or 2, P(O)(OR⁴)₂, straight-chain or branched C₁ -C₁₀-alkyl (e.g., methyl, ethyl, n- and isopropyl, n-, iso-, sec.-, andtert. -butyl, n-pentyl, neopentyl, n-hexyl, n-decyl ), C₁ -C₄ -haloalkyl(e. g., chloromethyl, bromomethyl, fluoromethyl, dichloromethyl,difluoromethyl, trifluoromethyl, 1,2-dibromoethyl,1,1,2,2-tetrafluoroethyl, pentafluoroethyl ), C₃ -C₆ -cycloalkyl(cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl),C₁ -C₄ -alkoxy-C₁ -C₄ -Alkyl (e.g., methoxymethyl, ethoxymethyl, tert.-butoxymethyl, methoxyethyl, ethoxyethyl, butoxyethyl), C₁ -C₄-alkylthio-C₁ -C₄ -alkyl (e.g., methylthiomethyl, methylthioethyl), C₂-C₆ -alkenyl (e.g., ethenyl, propen-1-yl, propen-2-yl, propen-3-yl,2-buten-2-yl), substituted or unsubstituted C₂ -C₆ -alkynyl (e.g.,ethynyl; methoxyethynyl, propynyl, 3-phenylethyn-1-yl,3-hydroxypropyn-1-yl, 3-chloropropyn-1-yl), C₁ -C₆ -alkoxy (e.g.,methoxy, ethoxy, n-and isopropoxy, n-, iso-, sec.-and tert.-butoxy), C₁-C₄ -alkylthio (e.g., methylthio), substituted or unsubstitutedbenzylthio (e.g., 2-chlorobenzylthio), C₁ -C₄ -alkylcarbonyl (e.g.,acetyl, ethylcarbonyl, isopropylcarbonyl), substituted or unsubstitutedphenylcarbonyl (e.g., 2-chlorophenylcarbonyl, 4-methylphenylcarbonyl),substituted or unsubstituted aryl, phenyl, naphthyl (e.g.,4-methylphenyl, 3-hydroxy-4-methylphenyl, 1-naphthyl,2-methyl-1-naphthyl), substituted or unsubstituted aryloxy (e.g.,phenoxy, 2-methylphenoxy, 4-chlorophenoxy, 3-nitrophenoxy), substitutedor unsubstituted arylthio (e.g., phenylthio), substituted orunsubstituted aryl-C₁ -C₄ -alkyl ( e. g., benzyl, 2 -chlorobenzyl,2,5-dimethoxybenzyl, phenethyl, 4-methylphenethyl), substituted orunsubstituted aryl-C₂ -C₄ -alkenyl (phenylethenyl,2-chlorophenylethenyl), substituted or unsubstituted aryl-C₂ -C₄-alkynyl (phenylethinyl, 4-methylphenylethynyl, 2-naphthylethynyl),substituted or unsubstituted aryloxy-C₁ -C₄ -alkyl (e.g., phenoxymethyl,2-CN-phenoxymethyl, 1-naphthyloxymethyl, phenoxyethyl), substituted orunsubstituted arylthio-C₁ -C₄ -alkyl (e.g., phenylthiomethyl),substituted or unsubstituted hetaryl (e.g., pyridyl, thienyl,2-chlorothien-5-yl), substituted or unsubstituted hetaryloxy (e.g.,2-pyridyloxy, 2-benzothienyloxy, 2-benzoxazolyloxy), substituted orunsubstituted hetaryl-C₁ -C₄ -alkyl (e.g., 4-pyridylmethyl,4-chloro-2-thienylmethyl), substituted or unsubstituted hetaryl-C₂ -C₄-alkenyl (e.g., 2-pyridylethenyl, 6-chloro-2-pyridylethenyl,2-thiazolylethenyl), substituted or unsubstituted hetaryloxy-C₁ -C₄-alkyl (e.g., 2-pyridyloxymethyl, 2-benzoxazolyloxymethyl,6-methyl-2-benzthiazolyloxymethyl), where "substituted or unsubstituted"means the radicals halogen, cyano, nitro, C₁ -C₄ -alkyl (e.g., methyl,ethyl), C₁ -C₄ -alkoxy (e.g., methoxy, ethoxy, tert.butoxy), C₁ -C₄-haloalkyl (e.g., trifluoromethyl), C₁ -C₄ -haloalkoxy (e.g.,trifluoromethoxy, C₁ -C₄ -alkoximino-C₁ -C₂ -alkyl (e.g.,methoximinomethyl, ethoximinomethyl, methoximinoethyl) and the termhetaryl has the abovementioned meanings, and

R¹, R², R³, R⁴, R⁵ are identical or different and each is hydrogen or C₁-C₄ -alkyl (e.g., methyl, ethyl, n- or isopropyl, or n-, iso-, sec- ortert. -butyl ) and

U, V, W are identical or different and each is hydrogen, halogen, C₁ -C₄-alkyl (e.g., methyl, ethyl, propyl, butyl) or C₁ -C₄ -alkoxy (e.g.,methoxy, ethoxy ).

Preferred compounds I are those in which A is ═CHOCH₃ or ═NOCH₃.

Compounds I in which B is methoxy or methylamino are also preferred.

Further, compounds I in which U, V and W are simultaneously hydrogen arepreferred.

Additionally, compounds I are preferred in which Het is a substituted orunsubstituted heterocyclic structure selected from the following group:thiazolyl, benzthiazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl andthienyl.

Particularly preferred compounds I are those in which Her is asubstituted or unsubstituted heterocyclic structure selected from thefollowing group: thiazol-2-yl, benzthiazol-2-yl, isoxazol-3-yl,1,3,4-thiadiazol-2-yl, 1,3,4-oxadiazol-2-yl and thien-2-yl.

Preferred substituents for Het are:

C₁ -C₆ -alkyl, which may be partially or completely halogenated (i.e.,in which the hydrogen atoms are partially or completely replaced byhalogen atoms selected from the group consisting of fluorine, chlorineand/or bromine) , and/or which may bear one of the following radicals:hydroxy, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylcarbonyloxy, phenyl, naphthyl,phenoxy, naphthyloxy, benzoyloxy, naphthoyloxy or thienyl, and thearomatic groups in turn may bear from one to three of the followingradicals: cyano, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄-alkoxy, C₁ -C₄ -haloalkoxy and C₁ -C₄ -alkylthio,

C₃ -C₈ -cycloalkyl, which may be partially halogenated and/or may bearfrom one to three of the following groups: C₁ -C₄ -alkyl, C₁ -C₄-haloalkyl, C₁ -C₄ -alkoxy and C₁ -C₄ -haloalkoxy,

C₂ -C₆ -alkoxy, which may be partially or completely halogenated (i.e.,in which the hydrogen atoms are partially or completely replaced byhalogen atoms selected from the group consisting of fluorine, chlorineand/or bromine), and/or which may bear one of the following radicals:phenyl, naphthyl, phenoxy, naphthyloxy, benzoyloxy, naphthoyloxy orthienyl, and the aromatic groups in turn may may be partially orcompletely halogenated and/or may bear from one to three of thefollowing radicals: cyano, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -haloalkyl, C₁-C₄ -alkoxy, C₁ -C₄ -haloalkoxy and C₁ -C₄ -alkylthio,

phenyl, imidazolyl, thienyl, benzothienyl and pyridyl, where thesegroups in turn may be partially or completely halogenated and/or maybear from one to three of the following radicals: cyano, nitro, C₁ -C₄-alkyl, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy and C₁ -C₄-alkylthio.

Preferred compounds are those in which

A is ═CHOCH₃ or ═NOCH₃

B is OCH₃ or NHCH₃,

U, V, W are hydrogen and

Het, R and R⁴, R⁵ have the meanings given above.

The novel compounds of the formula I are suitable as fungicides.

The novel compounds or agents containing them may be applied forinstance in the form of directly sprayable solutions, powders,suspensions (including high-percentage aqueous, oily or othersuspensions), dispersions, emulsions, oil dispersions, pastes, dusts,broadcasting agents, or granules by spraying, atomizing, dusting,broadcasting or watering. The forms of application depend entirely onthe purpose for which the agents are being used, but they must ensure asfine a distribution of the active ingredients according to the inventionas possible.

Normally, the plants are sprayed or dusted with the active ingredientsor the seeds of the plants are treated with the active ingredients.

Formulations are produced in known manner, for example by extending theactive ingredient with solvents and/or carriers, with or without the useof emulsifiers and dispersants; if water is used as solvent, it is alsopossible to employ other organic solvents as auxiliary solvents.Suitable auxiliaries for this purpose are solvents such as aromatics(e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins(e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones(e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide),and water; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as lignin-sulfitewaste liquors and methylcellulose.

Examples of surfactants are: alkali metal, alkaline earth metal andammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid,phenolsulfonic acid, naphthalenesulfonic acid anddibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, andsalts of sulfated hexadecanols, heptadecanols, and octadecanols, saltsof fatty alcohol glycol ethers, condensation products of sulfonatednaphthalene and naphthalene derivatives with formaldehyde, condensationproducts of naphthalene or naphthalenesulfonic acids with phenol andformaldehyde, polyoxyethylene octylphenol ethers, ethoxylatedisooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers,alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcoholethylene oxide condensates, ethoxylated castor oil, polyoxyethylenealkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycolether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

Powders, dusts and broadcasting agents may be prepared by mixing orgrinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may beprepared by bonding the active ingredients to solid carriers. Examplesof solid carriers are mineral earths such as silicic acids, silica gels,silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole,loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesiumsulfate, magnesium oxide, ground plastics, fertilizers such as ammoniumsulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetableproducts such as grain meals, bark meal, wood meal, and nutshell meal,cellulosic powders, etc.

Examples of formulations are given below.

I. A solution of 90 parts by weight of a compound according to theinvention and 10 parts by weight of N-methyl-d-pyrrolidone, which issuitable for application in the form of very fine drops.

II. A mixture of 20 parts by weight of a compound according to theinvention, 80 parts by weight of xylene, 10 parts by weight of theadduct of 8 to 10 moles of ethylene oxide and 1 mole of oleicacid-N-monoethanolamide, 5 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40moles of ethylene oxide and 1 mole of castor oil. By finely dispersingthe solution in water, a dispersion is obtained.

III. An aqueous dispersion of 20 parts by weight of a compound accordingto the invention, 40 parts by weight of cyclohexanone, 30 parts byweight of isobutanol, 20 parts by weight of the adduct of 40 moles ofethylene oxide and 1 mole of castor oil.

IV. An aqueous dispersion of 20 parts by weight of a compound accordingto the invention, 25 parts by weight of cyclohexanol, 65 parts by weightof a mineral oil fraction having a boiling point between 210° and 280°C., and 10 parts by weight of the adduct of 40 moles of ethylene oxideand 1 mole of castor oil.

V. A hammer-milled mixture of 80 parts by weight of a compound accordingto the invention, 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodiumsalt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and7 parts by weight of powdered silica gel. By finely dispersing themixture in water, a spray liquor is obtained.

VI. An intimate mixture of 3 parts by weight of a compound according tothe invention and 97 parts by weight of particulate kaolin. The dustcontains 3 wt % of the active ingredient.

VII. An intimate mixture of 30 parts by weight of a compound accordingto the invention, 92 parts by weight of powdered silica gel and 8 partsby weight of paraffin oil sprayed onto the surface of this silica gel.This formulation of the active ingredient exhibits good adherence.

VIII. A stable aqueous dispersion of 40 parts by weight of a compoundaccording to the invention, 10 parts of the sodium salt of aphenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica geland 48 parts of water, which dispersion can be further diluted.

IX. A stable oily dispersion of 20 parts by weight of a compoundaccording to the invention, 2 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcoholpolyglycol ether, 20 parts by weight of the sodium salt of aphenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weightof a paraffinic mineral oil.

The novel compounds are extremely effective on a broad spectrum ofphytopathogenic fungi, in particular those from the class consisting ofthe Ascomycetes and Basidiomycetes. Some of them have a systemic actionand may be used as foliar and soil fungicides.

The compounds are of particular interest for controlling a large numberof fungi in various crops or their seeds, especially wheat, rye, barley,oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane,fruit and ornamentals in horticulture and viticulture, and in vegetablessuch as cucumbers, beans and cucurbits.

The compounds are applied by treating the seeds, plants, materials orsoil to be protected against fungus attack with a fungicidally effectiveamount of the active ingredients.

The compounds may be applied before or after infection of the materials,plants or seeds by the fungi.

The novel compounds are particularly useful for controlling thefollowing plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia solani in cotton,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in fruit and vegetables.

The novel compositions may also be used for protecting materials(timber), for example against Paecilomyces variotii.

The fungicidal agents generally contain from 0.1 to 95, and preferablyfrom 0.5 to 90, wt % of active ingredient.

The application rates depend on the type of effect desired, but aregenerally from 0.02 to 3 kg of active ingredient composition perhectare.

When the compositions are used for treating seed, application rates offrom 0.001 to 50, and preferably from 0.01 to 10, g per kg of seed aregenerally required.

In these application forms, the agents according to the invention mayalso be present together with other active ingredients, for exampleherbicides, insecticides, growth regulators, and other fungicides, andmay furthermore be mixed and applied together with fertilizers.Admixture with other fungicides frequently results in a greaterfungicidal action spectrum.

The following list of fungicides with which the novel compounds may becombined is intended to illustrate possible combinations but not toimpose any restrictions.

Examples of fungicides which may be combined with the novel compoundsare:

sulfur,

dithiocarbamates and their derivatives, such as

ferric dimethyldithiocarbamate,

zinc dimethyldithiocarbamate,

zinc ethylenebisdithiocarbamate,

manganese ethylenebisdithiocarbamate,

manganese zinc ethylenediaminebisdithiocarbamate,

tetramethylthiuram disulfides,

ammonia complex of zinc N,N'-ethylenebisdithiocarbamate,

ammonia complex of zinc N,N'-propylenebisdithiocarbamate,

zinc N,N'-propylenebisdithiocarbamate and

N,N'-polypropylenebis(thiocarbamyl) disulfide;

nitro derivatives, such as

dinitro(1-methylheptyl)-phenyl crotonate,

2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,

2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and

diisopropyl 5-nitroisophthalate;

heterocyclic substances, such as

2-heptadecylimidazol-2-yl acetate,

2,4-dichloro-6-(o-chloroanilino)-s-triazine,

O,O-diethyl phthalimidophosphonothioate,

5-amino-1- -bis-(dimethylamino)-phosphinyl!-3-phenyl-1,2,4-triazole,

2,3-dicyano-1,4-dithioanthraquinone,

2-thio-1,3-dithio 4,5-b!quinoxaline,

methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate,

2-methoxycarbonylaminobenzimidazole,

2-(fur-2-yl)-benzimidazole,

2-(thiazol-4-yl)benzimidazole,

N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide,

N-trichloromethylthiotetrahydrophthalimide,

N-trichloromethylthiophthalimide,

N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide,

5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,

2-thiocyanatomethylthiobenzothiazole,

1,4-dichloro-2,5-dimethoxybenzene,

4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,

2-thiopyridine 1-oxide,

8-hydroxyquinoline and its copper salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide,

2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,

2-methylfuran-3-carboxanilide,

2,5 -dimethylfuran-3-carboxanilide,

2,4,5-trimethylfuran-3-carboxanilide,

2,5-dimethyl-N-cyclohexylfuran-3-carboxamide,

N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide,

2-methylbenzanilide,

2-iodobenzanilide,

N-formyl-N-morpholine-2,2,2-trichloroethylacetal,

piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide),

1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,

2,6-dimethyl-N-tridecylmorpholine and its salts,

2,6-dimethyl-N-cyclododecylmorpholine and its salts,

N 3-(p-tert.-butylphenyl)-2-methylpropyl!-cis-2,6-dimethylmorlpholine,

N-3-(p-tert.-butylphenyl)-2-methylpropyl'-piperidine,

1-2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl'-1H-1,2,4-triazole

1-2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl-ethyl!-1H-1,2,4-triazole,

N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea,

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-tri-azol-1-yl)butan-2-one,

1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1, 2,4-triazol-1-yl)butan-2-ol,

α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,

5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine,

bis-(p-chlorophenyl)-3-pyridinemethanol,

1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene,

1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene,

and various fungicides, such as

dodecylguanidine acetate,

3- 3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl!-glutaramide,

hexachlorobenzene,

DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate,

methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)-alan-ate,

N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone,

methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate,

5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,

3-3,5-dichlorophenyl!-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,

3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin,

N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,

2-cyano- N-(ethylaminocarbonyl)-2-methoximino!-acetamide,

1- 2-(2,4-dichlorophenyl)-pentyl!-1H-1,2,4-triazole,

2,4-difluoro-α-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol,

N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,and

1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-1H-1,2,4-triazole.

SYNTHESIS EXAMPLES

The directions given in the synthesis examples below were used, afterappropriate modification of the starting materials, to obtain furthercompounds I. The compounds thus obtained are given in the tables belowtogether with their physical data.

Example 1 o-Formylphenylglyoxylic Acid Methyl ester-O-methyloxime(Compound A)

32 g (0.236 mol) of N-methylmorpholine-N-oxi.H₂ O20 g is added to asolution of 20 g (0.07 mol) of 2-bromomethylphenylglyoxylic acid methylester-O-methyloxime in 300 ml of CCl₄. The mixture is refluxed for 4hours and then allowed to cool. It is washed with water and 10% strengthhydrochloric acid, dried and evaporated down. After chromatography onsilica gel using cyclohexane/ethyl acetate there remains 9.5 g (61% ofaldehyde (A) as a colorless solid.

¹ H-NMR (CDCl₃ /TMS): δ=3.86, 4.01 (s,3H), 7.32-7.93 (m,4H), 9.88 ppm(s,1H).

Example 2 2-(Formylhydroxylamino)phenylglyoxylic Acid MethylEster-O-methyloxime (Compound B)

At 60°-70° C., 10 g (45 mmol) of aldehyde A is added in portions to asolution of 7.15 g (67.5 mmol) of Na₂ CO₃ and 4.7 g (67.5 mmol) ofhydroxylamine hydrochloride in 50 ml of isopropanol. After all has beenadded, the mixture is allowed to cool and is stirred overnight at roomtemperature. The mixture is evaporated down, and the residue is taken upin ethyl acetate, washed with water, dried and evaporated down. Afterchromatography using cyclohexane/ethyl acetate there remains 7.5 g (71%)of oxime (B).

¹ H-NMR (CDCl₃ /TMS):δ=3.86, 4.03 (s,3H), 7.20-7.68 (m, 4H), 8.00(s,1H), 8.34 ppm (br, 1H).

Example 3 2-Hydroxylcarbonylphenylglyoxylic Acid MethylEster-O-methyloxime (Compound C)

A mixture of 10 g (45 mmol) of compound A, 5.5 g (55 mmol) of chromiumtrioxide and 100 ml of conc. acetic acid is stirred at 50° C. for 2hours. The mixture is allowed to cool, and is then diluted with water,extracted with ethyl acetate, dried and evaporated down. There remains9.9 g (92.5%) of benzoic acid C as an oil.

¹ H-NMR (DMSO-d⁶): δ=3.70, 3.89 (s,3H), 7.28-7.89 (m,4H), 12.8 ppm (br,1H).

Example 4 2-Chlorocarbonylphenylglyoxylic Acid MethylEster-O-methyloxime (Compound D)

At -10° to 0° C., 1.1 g (9.3 mmol) of thionyl chloride is dripped into asolution of 2 g (8.43 mmol) of benzoic acid C and 1.3 g (16.40 mmol) ofpyridine in 20 ml-of methyl-tert.-butyl ether and 10 ml of methylenechloride. The mixture is allowed to warm up to room temperature and isthen stirred overnight at room temperature (R_(T)). The solvent is thenremoved under reduced pressure. The crude product can be used in thisform for further reactions.

Example 5 2-Bromophenylglyoxylic Acid Methyl Ester-O-methyloxime(Compound E)

5.2 g (62 mmol) of O-methylhydroxylamine hydrochloride is added to asolution of 10 g (41 mmol) of methyl 2-bromophenylglyoxylate in 30 ml ofmethanol, and the mixture is refluxed for 2 hours. The mixture isevaporated down, and the residue is taken up in ethyl acetate and washedwith water. After drying and evaporating down, there remains 6.9 g (62%)of compound E.

¹ H-NMR (CDCl₃ /TMS) δ=3.88, 4.07 (s,3H), 7.17-7.61 ppm (m,4H).

Example 6 2-Ethynylphenylglyoxylic Acid Methyl Ester-O-methyloxime(Compound F)

33.3 g (0.35 mol) of trimethylsilylacetylene, 3.8 g of palladium(II)acetate, 3.2 g of copper(I) iodide and 8.9 g of triphenylphosphine areadded to a solution of 55.4 g (0.23 mol) of methyl2-bromophenylglyoxylate in 415 ml of triethylamine, and nitrogen ispassed through the solution for 30 minutes. The reaction mixture is thenheated for 45 minutes at 90° C. The mixture is cooled and filtered. Thefiltrate is evaporated down, taken up in ethyl acetate and washed withwater. The organic phase is dried and evaporated down. There remains56.8 g of the α-keto ester as a black oil.

The crude product prepared in this way is dissolved in 50 ml ofmethanol, 38.9 g (0.37 mol) of O-methylhydroxylamine hydrochloride isadded and the mixture is heated for 15 minutes at 60° C. The mixture isevaporated down, and the residue is taken up in ethyl acetate and washedwith water. The organic phase is dried and evaporated down. Thereremains 52.4 g of the trimethylsilyl compound as a black oil.

¹ H-NMR (CDCl₃ /TMS): δ=0.22 (s,9H, SiMe₃); 3.86; 4.06 (s,3H,OCH₃);7.25-7.61 ppm (m, 4H,aryl).

The trimethylsilylacetylene compound prepared in this way is dissolvedin 320 ml of methanol and stirred with 3.2 g of potassium carbonate for1 hour at room temperature (20° C.). The mixture is evaporated down, andthe residue is taken up in methylene chloride and washed with 10%strength sodium bicarbonate solution. The organic phase is dried andevaporated down. There remains 36 g (72%, based on methyl2-bromophenylglyoxylate) of compound F as a black solid.

¹ H-NMR (CDCl₃ /TMS): δ=3.17 (s,3H,.tbd.C--H); 3.87; 4.07 (s,3H,OCH₃);7.27-7.60 ppm (m, 4H,aryl).

Example 7 2(5-Phenylisoxazol-3-yl)-Phenylglyoxylic Acid MethylEster-O-methyloxime (Compound 37, Tab. I)

5.7 g (7.6 mmol) of sodium hypochlorite and 3 drops of dilute NaOH areadded to 700 mg (7.6 mmol) of phenylacetylene and 1.2 g (5 mmol) ofcompound B in 20 ml of methylene chloride, and the mixture is stirredovernight at room temperature. The methylene chloride phase is separatedoff and evaporated down. After chromatography on silica gel usingcyclohexane/ethyl acetate, there is obtained 700 mg (42%) of compound37, Tab. I, as an oil.

¹ H-NMR (CDCl₃ /TMS): δ=3.80, 4.01 (s,3H), 6.67 (s,2H), 7.35-7.80 ppm(m, 9H).

Example 8 2 3-(2-Methylphenyl)-isoxazol-5-yl!-phenylglyoxylic AcidMethyl Ester-O-methyloxime (Compound 38, Tab. I)

4.5 g of sodium hypochlorite is added to 1 g (3.15 mmol) of compound Fand 600 mg (4.73 mmol) of 2-methylbenzaldehyde oxime in 50 ml ofmethylene chloride, and the whole is stirred for 1 hour at roomtemperature. The organic phase is separated off, dried and evaporateddown. After chromatography on silica gel there is obtained 1 g ofcompound 38, Tab. I, as an oil.

¹ H-NMR (CDCl₃ /TMS): δ=2.48, 3.79, 4.02 (S,3H), 6.52(S,1H), 7.26-7.94ppm (8H).

Example 9 2 5-(3-Methylphenyl)-1,3,4-oxadiazol-2-yl!-phenylglyoxylicAcid Methyl Ester-O-methyloxime (Compound 50, Tab. I)

a) 2 g (13.6 mmol) of 3-methylphenylhydrazone is added to a solution of3 g (13.6 mmol) of compound A in 100 ml of methanol, and the whole isstirred overnight at room temperature. The precipitated solid is suctionfiltered, washed with diisopropyl ether and dried under reducedpressure. There is obtained 3.6 g (75%) of the iminohydrazone as asolid. M.p.: 231°-232° C.

b) 4.2 g (9.5 mmol) of lead tetraacetate is added to a solution of 1.6 g(4.5 mmol) of the iminohydrazone compound prepared under a) in 100 ml ofchloroform, and the whole is stirred overnight at room temperature. 750ml of water is added, and the organic phase is separated off, dried andevaporated down. There remains 1.5 g (95%) of compound 50, Tab. I, as asolid. M.p.: 166°-167° C.

Example 10 2(Thiazol-2-yl)phenylglyoxylic Acid MethylEster-O-methyloxime (Compound 1, Tab. I)

Under a nitrogen blanket, 1.7 g of 2-triethylstannylthiazole is added toa mixture of 1.4 g (5.19 mmol) of the bromo compound (Compound E), 100mg of palladium(II) chloride and 310 mg of triphenylphosphine in 30 mlof tetrahydrofuran, and the whole is refluxed for 2 hours. The mixtureis then filtered and evaporated down. After chromatography on silica gelusing cyclohexane/ethyl acetate there remains 700 mg (49%) of compound1, Tab. I, as an oil.

¹ H-NMR (CDCl₃ /TMS) δ=3.75, 3.97 (s,3H), 7.28-7.86 ppm (m, 6H).

Example 11 2 5-Cyclohexyl-1,3,4-thiadiazol-2-yl!-phenylglyoxylic AcidMethyl Ester-O-methyloxime (Compound 48, Tab. I)

At 0° C. 3.6 g of methyl dithiocyclohexanecarboxylate in 25 ml ofmethanol is added to a solution of 2.1 g of hydrazine hydrate in 7 ml ofwater. The mixture is stirred for 10 minutes and is then poured into 100ml of water. It is then neutralized with 10% strength hydrochloric acid,extracted with methyl tert.-butyl ether, dried and evaporated down. Theresidue is taken up in 50 ml of acetonitrile. At 0° C. a solution of 5.5g (23 mmol) of compound D in 30 ml of acetonitrile is dripped in, andthe mixture is refluxed for 2 hours. Methylene chloride is then added,and the mixture is washed with saturated NaHCO₃ solution and with water,dried and evaporated down.

After chromatography on silica gel using cyclohexane/ethyl acetate thereremains 3.5 g (49%) of compound 48, Tab. I, as an oil.

¹ H-NMR (CDCl₃ /TMS) δ=1.26-3.21 (m, 11H), 3.81, 3.96 (s,3H) 7.30-7.81ppm (m, 4H) .

Example 12 2 Benzthiazol-2-yl!-phenylglyoxylic Acid MethylEster-O-methyloxime (Compound 2, Tab. I)

a) Under a nitrogen blanket and at -78° C., 1.5 equivalents of n-BuLi isdripped into a solution of 2 g (6.9 mmol) of2-Benzthiazol-2-yl-bromobenzene in 20 ml of THF. The mixture is stirredfor 1 hour at this temperature, after which 1.6 g of dimethyl oxalate in20 ml of THF is added. The mixture is allowed to warm up, water is addedand the mixture is extracted with methyl tert-butyl ether. Afterchromatography on silica gel using hexane/methyl tert.-butyl ether thereremains 300 mg (15%) of the corresponding phenyl keto ester.

¹ H-NMR (CDCl₃ /TMS): δ=3.56 (s,3H), 7.38-8.01 ppm (m, 8H).

b) 1 g of methoxyamine hydrochloride is added to a solution of the ketoester prepared in this way in 5 ml of methanol. The mixture is stirredfor 1 hour and evaporated down. Chromatography on silica gel usinghexane/methyl tert.-butyl ether gives 100 mg of compound 2, Tab. I, as agray solid.

¹ H-NMR (CDCl₃ /TMS): δ=3.76, 3.99 (s,3H), 7.35-8.03 ppm (m, 8H).

                  TABLE I                                                         ______________________________________                                         ##STR15##                                                                                           Phys. data; H-NMR  δ, ppm!,                      No.  Het               IR cm.sup.-1 !; m.p.  °C.!                      ______________________________________                                         1   Thiazol-2-yl      3.75; 3.97(s, 3H); 7.28-7.86(m,                                               6H)                                                     2   Benzthiazol-2-yl  3.76; 3.99(s, 3H); 7.35-8.03(m,                                               8H)                                                     3   Thien-2-yl                                                                4   Benzthien-2-yl                                                            5   Furan-2-yl                                                                6   Furan-3-yl                                                                7   Benzofuran-2-yl                                                           8   Benzofuran-3-yl                                                           9   Imidazol-2-yl                                                            10   Benzimidazol-2-yl                                                        11   Pyrrol-2-yl                                                              12   N-Methyl-pyrrol-2-yl                                                     13   Pyridin-2-yl                                                             14   Pyridin-3-yl                                                             15   Pyridin-4-yl                                                             16   Quinolin-2-yl                                                            17   6-Chloropyridin-2-yl                                                     18   4-Methyl-pyridin-2-yl                                                    19   Oxazol-2-yl                                                              20   Benzoxazol-2-yl                                                          21   4-Phenyl-oxazol-2-yl                                                     22   5-Phenyl-oxazol-2-yl                                                     23   5-Methyl-isoxazol-3-yl                                                   24   5-Bromomethyl-isoxazol-3-yl                                                                     3.81; 3.99(s, 3H); 4.48(s, 2H);                                               6.45; (s, 1H); 7.32-7.71(m, 4H)                        25   5-Hydroxymethyl-isoxazol-3-yl                                                                   3490, 1717, 1370, 1255, 1081,                                                 1068, 1023, 953, 778                                   26   5-Acyloxymethyl-isoxazol-3-yl                                                                   2.13; 3.81; 3.99(s, 3H); 5.18(s,                                              2H); 6.47(s, 1H); 7.32-7.71(m,                                                4H)                                                    27   5-(2-Methyl)phenyloxymethyl-                                                                    2.25; 3.77; 3.95(s, 3H); 5.14(s,                            isoxazol-3-yl     2H); 6.47(s, 1H); 6.84-7.70(m,                                                8H)                                                    28   5-(2,5-Dimethyl)phenyloxy-                                                                      2.20; 2.32; 3.77; 3.96(s, 3H);                              methyl-isoxazol-3-yl                                                                            5.14(s, 2H); 6.47(s, 1H); 6.67-                                               7.71(m, 7H)                                            29   5-tert.-Butyl-isoxazol-3-yl                                                                     1.36(s, 9H); 3.77; 3.96(s, 3H);                                               6.09(s, 1H); 7.30-7.70(m, 4H)                          30   5-Cyclohexyl-isoxazol-3-yl                                                                      1.13-2.85(m, 11H); 3.78; 3.99                                                 (s, 3H); 6.11(s, 1H); 7.30-7.71                                               (m, 4H)                                                31   5-Pentyl-isoxazol-3-yl                                                                          0.71-2.75(m, 11H); 3.79; 4.00                                                 (s, 3H); 6.11(s, 1H); 7.30-7.71                                               (m, 4H)                                                32   5- 1-(4-Nitrophenoxy)ethyl!-                                                                    1.80(d, 3H); 3.76; 3.94(s, 3H);                             isoxazol-3-yl     5.60(q, 1H); 6.37(s, 1H); 6.97-                                               8.21(m, 8H)                                            33   5-Benzoyloxymethyl-isoxazol-3-                                                                  3.79; 3.97(s, 3H); 5.43(s, 2H);                             yl                6.54(s, 1H); 7.28-8.08(m, 9H)                          34   5-β-Naphthyloxymethylisoxazol-                                                             3.74; 3.92(s, 3H); 5.25(s, 2H);                             3-yl              6.53(s, 1H); 7.18-7.78(m, 11H)                         35   5-α-Naphthyloxymethyliso-                                                                 3.77; 3.96(s, 3H); 5.35(s, 2H);                             xazol-3-yl        6.57(s, 1H); 6.85-8.28(m, 11H)                         36   5-Thiophenylmethylisoxazol-3-                                                                   3.75; 3.93(s, 3H); 4.13(s, 2H);                             yl                6.22(s, 1H); 7.20-7.63(m, 9H)                          37   5-Phenyl-isoxazol-3-yl                                                                          3.80; 4.01(s, 3H); 6.67(s, 1H);                                               7.35-7.80(m, 9H)                                       38   3-(2-Methyl)phenyl-isoxazol-5-                                                                  2.48; 3.79; 4.02(s, 3H); 6.52(s,                            yl                1H); 7.26-7.94(m, 8H)                                  39   3-Phenyl-isoxazol-5-yl                                                                          3.79; 4.02(s, 3H); 6.65(s, 2H);                                               7.32-7.88(m, 9H)                                       40   5-(2-Methyl)phenyl-isoxazol-3-                                                                  2.52; 3.79; 4.01(s, 3H), 6.55(s,                            yl                1H); 7.28-7.70(m, 8H)                                  41   5-(1-tert.-Butoxy)ethylisoxazol-                                                                1.22(s, 9H); 1.47(d, 3H); 3.77;                             3-yl              3.96(s, 3H); 4.78(q, 1H); 6.31(s,                                             1H); 7.30-7.70(m, 4H)                                  42   5-n-Propyl-isoxazol-3-yl                                                                        0.99(t, 3H); 1.74(m, 2H); 2.73(t,                                             2H); 3.77; 3.97(s, 3H); 6.10(s,                                               1H); 7.28-7.68(m, 4H)                                  43   5-(2-Acetyloxy)isopropyl-                                                                       1.80(s, 6H); 2.04; 3.79; 3.97(s,                            isoxazol-3-yl     3H); 6.29(s, 1H); 7.28-7.70(m,                                                4H)                                                    44   5-Cyclooctyl-isoxazol-3-yl                                                                      1.22-2.12(m, 15H); 3.77; 3.97                                                 (s, 3H); 6.31(s, 1H); 7.30-7.70                                               (m, 4H)                                                45   3-tert.-Butyl-isoxazol-5-yl                                                                     1.34(s, 9H); 3.76; 4.01(s, 3H);                                               6.26(s, 1H); 7.30-7.84(m, 4H)                          46   3-Cyclohexyl-isoxazol-3-yl 5                                                                    1.26-2.81(m, 11H); 3.76; 4.01                                                 (s, 3H); 6.20(s, 1H); 7.30-7.83                                               (m, 4H)                                                47   5-α-Methoxybenzyl-isoxazol-3-                                                             3.43; 3.71; 3.91(s, 3H); 5.36;                              yl                6.30(s, 1H); 7.28-7.66(m, 9H)                          48   5-Cyclohexyl-1,3,4-thiadiazol-2-                                                                1.26-3.21(m, 11H); 3.81; 3.96                               yl                (s, 3H); 7.30-7.81(m, 4H)                              49   5-Phenyl-1,3,4-oxadiazol-2-yl                                                                   160-161° C.                                     50   5-(3-Methyl)phenyl-1,3,4-oxa-                                                                   166-167° C.                                          diazol-2-yl                                                              51   5-(4-Cyano)phenyl-1,3,4-oxa-                                                                    188-189° C.                                          diazol-2-yl                                                              52   5-(4-Chloro)phenyl-1,3,4-oxa-                                                                   161-162° C.                                          diazol-2-yl                                                              53   5-(3,4,5-Trimethoxy)phenyl-                                                                     136-144° C.                                          1,3,4-oxadiazol-2-yl                                                     54   5-(5-Methyl)imidazol-4-yl-1,3,4-                                                                198° C. (decomp.)                                    oxadiazol-2-yl                                                           55   5-Thien-2-yl-1,3,4-oxadiazol-2-                                                                 196-197° C.                                          yl                                                                       56   5-Pyridin-3-yl-1,3,4-oxadiazol-                                                                 168-170° C.                                          2-yl                                                                     57   5-Benzothien-2-yl-1,3,4-oxa-                                                                    209-213° C.                                          diazol-2-yl                                                              58   5-(3-Chloro)benzothien-2-yl-                                                                    205-206° C.                                          1,3,4-oxadiazol-2-yl                                                     59   5-Furan-2-yl-1,3,4-oxadiazol-2-                                                                 162-170° C.                                          yl                                                                       60   5- (3-Methoxy-5-thien-2-yl)-                                                                    3.68; 3.88; 4.04(s, 3H); 6.92-                              phenyl!thien-2-yl 7.58(m, 12H)                                           ______________________________________                                    

                  TABLE II                                                        ______________________________________                                         ##STR16##                                                                    No.   Het                      Phys. data                                     ______________________________________                                         1    Thiazol-2-yl                                                             2    Benzthiazol-2-yl                                                         3    Thien-2-yl                                                               4    Benzthien-2-yl                                                           5    Furan-2-yl                                                               6    Furan-3-yl                                                               7    Benzofuran-2-yl                                                          8    Benzofuran-3-yl                                                          9    Imidazol-2-yl                                                           10    Benzimidazol-2-yl                                                       11    Pyrrol-2-yl                                                             12    N-Methyl-pyrrol-2-yl                                                    13    Pyridin-2-yl                                                            14    Pyridin-3-yl                                                            15    Pyridin-4-yl                                                            16    Quinolin-2-yl                                                           17    6-Chloropyridin-2-yl                                                    18    4-Methyl-pyridin-2-yl                                                   19    Oxazol-2-yl                                                             20    Benzoxazol-2-yl                                                         21    4-Phenyl-oxazol-2-yl                                                    22    5-Phenyl-oxazol-2-yl                                                    23    5-Methyl-isoxazol-3-yl                                                  24    5-Bromomethyl-isoxazol-3-yl                                             25    5-Hydroxymethyl-isoxazol-3-yl                                           26    5-Acyloxymethyl-isoxazol-3-yl                                           27    5-(2-Methyl)phenyloxymethyl-isoxazol-3-yl                               28    5-(2,5-Dimethyl)phenyloxy-methyl-isoxazol-3-yl                          29    5-tert.-Butyl-isoxazol-3-yl                                             30    5-Cyclohexyl-isoxazol-3-yl                                              31    5-Pentyl-isoxazol-3-yl                                                  32    5- 1-(4-Nitrophenoxy)ethyl!-isoxazol-3-yl                               33    5-Benzoyloxymethyl-isoxazol-3-yl                                        34    5-β-Naphthyloxymethyl-isoxazol-3-yl                                35    5-α-Naphthyloxymethyl-isoxazol-3-yl                               36    5-Thiophenylmethyl-isoxazol-3-yl                                        37    5-Phenyl-isoxazol-3-yl                                                  38    3-(2-Methyl)phenyl-isoxazol-5-yl                                        39    3-Phenyl-isoxazol-5-yl                                                  40    5-(2-Methyl)phenyl-isoxazol-3-yl                                        41    5-(1-tert.-Butoxy)ethyl-isoxazol-3-yl                                   42    5-n-Propyl-isoxazol-3-yl                                                43    5-(2-Acetyloxy)isopropyl-isoxazol-3-yl                                  44    5-Cyclooctyl-isoxazol-3-yl                                              45    3-tert.-Butyl-isoxazol-5-yl                                             46    3-Cyclohexyl-isoxazol-5-yl                                              47    5-α-Methoxybenzyl-isoxazol-3-yl                                   48    5-Cyclohexyl-1,3,4-thiadiazol-2-yl                                      49    5-Phenyl-1,3,4-oxadiazol-2-yl                                           50    5-(3-Methyl)phenyl-1,3,4-oxadiazol-2-yl                                 51    5-(4-Cyano)phenyl-1,3,4-oxadiazol-2-yl                                  52    5-(4-Chloro)phenyl-1,3,4-oxadiazol-2-yl                                 53    5-(3,4,5-Trimethoxy)phenyl-1,3,4-oxadiazol-2-yl                         54    5-(5-Methyl)imidazol-4-yl-1,3,4-oxadiazol-2-yl                          55    5-Thien-2-yl-1,3,4-oxadiazol-2-yl                                       56    5-Pyridin-3-yl-1,3,4-oxadiazol-2-yl                                     57    5-Benzothien-2-yl-1,3,4-oxadiazol-2-yl                                  58    5-(3-Chloro)benzothien-2-yl-1,3,4-oxadiazol-2-yl                        59    5-Furan-2-yl-1,3,4-oxadiazol-2-yl                                       60    5- (3-Methoxy-5-thien-2-yl)phenyl!thien-2-yl                            ______________________________________                                    

Use Examples

For the following use examples, the compounds used for comparisonpurposes were 2-(2-phenylphenyl)-glyoxylic acid methylester-O-methyloxium (A)--corresponds to EP-A 254 426--and methyl2-(2-phenylphenyl)-3-methoxyacrylate (B)--disclosed in EP-A 178 826.

Use Example 1 Action on Plasmopara Viticola

Leaves of potted vines of the Muller-Thurgau variety were sprayed withaqueous suspensions containing (dry basis) 80% of active ingredient and20% of emulsifier. To assess the duration of action, the plants were setup, after the sprayed-on layer had dried, for 8 days in the greenhouse.Then the leaves were infected with a zoospore suspension of Plasmoparaviticola. The plants were first placed for 48 hours in a watervapor-saturated chamber at 24° C. and then in a greenhouse for 5 days atfrom 20° to 30° C. To accelerate and intensify the sporangiophoredischarge, the plants ere then again placed in the moist chamber for 16hours. The extent of fungus attack was then assessed on the undersidesof the leaves.

The results show that compounds nos. 21, 32, 37, 38, 39, 40 and 45 fromTable I, when employed as spray liquors containing 63 ppm of activeingredient, have a better fungicidal action (95%) than prior art activeingredients A and B (70%).

Use Example 2 Action on Pyricularia oryzae (Protective)

Leaves of pot-grown rice seedlings of the "TaiNong" variety were sprayedto runoff with aqueous emulsions containing (dry basis) 80% of activeingredient and 20% of emulsifier, and inoculated 24 hours later with anaqueous spore suspension of Pyricularia oryzae. The plants were then setup in climatic cabinets at 22° to 24° C. and 95 to 99% relativehumidity. The extent of fungus attack was assessed after 6 days.

The results show that compounds nos. 29, 40, 41, 42, 43, 44, 45, 46 and50, when applied as spray liquors containing 250 ppm of activeingredient, have a better fungicidal action (85%) than prior art activeingredient A (20%).

We claim:
 1. A method of combatting insects, nematodes, or mites,comprising:applying to insects, nematodes or mites, or their habitats, apesticidally effective amount of a diaryl derivative of formula I:##STR17## where: A is ═CHOR¹, ═CHSR¹, ═CHR¹, ═CHCl or ═NOR¹, B is OR²,SR² or NR² R³, Het is a mono-, or dinuclear, five- or six-memberedheterocylic structure which may carry from one to three radicals R,wherein R is halogen, nitro, cyano, CO₂ R⁴, NR⁴ R⁵, CONR⁴ R⁵, S(O)_(n)R⁴ P(O)(OR⁴)₂, substituted or unsubstituted C₁ -C₆ -alkyl, C₁ -C₄-haloalkyl, substituted or unsubstituted C₃ -C₆ -cycloalkyl, C₁ -C₄-alkoxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio-C₁ -C₄ -alkyl, substituted orunsubstituted C₂ -C₆ -alkenyl, substituted or unsubstituted C₂ -C₆-alkynyl, C₁ -C₆ -alkoxy, C₁ -C₄ -thioalkoxy, substituted orunsubstituted benzylthio, C₁ -C₄ -alkylcarbonyl, substituted orunsubstituted phenylcarbonyl, substituted or unsubstituted aryl,substituted or unsubstituted aryloxy, substituted or unsubstitutedarylthio, substituted or unsubstituted aryl-C₁ -C₄ -alkyl, substitutedor unsubstituted aryl-C₂ -C₄ -alkenyl, substituted or unsubstitutedaryl-C₂ -C₄ -alkynyl, substituted or unsubstituted aryloxy-C₁ -C₄-alkyl, substituted or unsubstituted arylthio-C₁ -C₄ -alkyl, substitutedor unsubstituted hetaryl, substituted or unsubstituted hetaryloxy,substituted or unsubstituted hetaryl-C₁ -C₄ -alkyl, substituted orunsubstituted hetaryl-C₂ -C₄ - alkenyl, substituted or unsubstitutedhetaryloxy-C₁ -C₄ -alkyl, "substituted or unsubstituted" denoting theradicals halogen, cyano, nitro, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-haloalkyl, C₁ -C₄ -haloalkoxy or C₁ -C₄ -alkoximino-C₁ -C₂ -alkyl andwherein n is 0, 1 or 2; R¹, R², R³, R⁴, R⁵ are identical or differentand each is hydrogen or C₁ -C₄ -alkyl; and U, V, W are identical ordifferent and each is halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.
 2. Themethod of claim 1, wherein A is NOCH₃, B is OCH₃, Het is isoxazolyl-3, Ris 5-phenyl and U, V, W are hydrogen.
 3. The method of claim 1, whereinA is NOCH₃, B is OCH₃, Het is isoxazolyl-5, R is 3-(2-methylphenyl) andU, V, W are hydrogen.
 4. The method of claim 1, wherein A is NOCH₃, B isOCH₃, Het is 1,3,4-oxadiazolyl-2, R is 5-(3-methylphenyl) and U, V, Ware hydrogen.
 5. The method of claim 1, wherein A is NOCH₃, B is OCH₃,Het is thiazolyl-2 an U, V, W are hydrogen.
 6. The method of claim 1,wherein A is NOCH₃, B is OCH₃, Het is 1,3,4-thiadiazolyl-2, R is5-cyclohexyl and U, V, W are hydrogen.
 7. The method of claim 1, whereinA is NOCH₃, B is OCH₃, Het is benzthiazolyl-2 and U, V, W are hydrogen.8. The method of claim 1, wherein A is NOCH₃, B is OCH₃, Het is5-(3-chloro)benzothien-2-yl-1,3,4-oxadiazol-2-yl and each of U, V and Wis hydrogen.
 9. The method of claim 1, wherein Het is isoxazolyl-3,isoxazolyl-5, 1,3,4-oxadiazolyl-2, thiazol-2, 1,3,4-thiadiazolyl-2 orbenzthiazolyl-2.
 10. The method of claim 1, wherein Het carries at leastone radical R which is unsubstituted or substituted aryl orunsubstituted or substituted hetaryl.
 11. The method of claim 1, whereinA is ═NOCH₃.
 12. The method of claim 1, wherein B is --OCH₃ or --NHCH₃.